SU1549963A1 - Method of obtaining o-(2-aryloxycarbonylphenyl) phosphonites - Google Patents

Abstract

The invention relates to the chemistry of organophosphorus compounds, in particular the preparation of O- (2-aryloxycarbonylphenyl) phosphonites of the general formula XC ₆ H ₃ [C (O) OAR] -OP (O) HR, where XH, alkyl, halo

R-aryl, aralkyl

AR is a non - or substituted phenyl, which can be used to synthesize organophosphorus substances and active pesticidal compounds. The goal is to simplify the process and expand the range of target substances. Synthesis is carried out by the reaction of equimolar amounts of organo-dichlorophosphine and phenol in the presence of 1 mol.% Pyridine in a solution of tert-butyl chloride with salicylic or substituted salicylic acid at the boiling point of tert-butyl chloride. Meaning: X

AR

R

output,%

N ²⁰

bp, ° C / mmHg

gross l: a) H

4-CH ₃ C ₆ H ₄

C ₆ H ₅

100

1.5902

217/4

C ₂₀ H ₁₇ O ₄ P

b) H

C ₆ H ₅

99.7

1.6043

215/2

C ₁₉ H ₁₅ O ₄ P

c) H, 4-CLC ₆ H ₄ , C ₆ H ₅

99.8

1.6068

-

C ₁₉ H ₁₄ CLO ₄ P

d) H

2,4,5-CL ₃ C ₆ H ₂

C ₆ H ₅

99

-

m.p. 142-144

C ₁₉ H ₁₂ CL ₃ O ₄ P

d) 3-CH ₃

C ₆ H ₅

100

1.5954

-

C ₂₀ H ₁₇ O ₄ P

e) 5-CL

C ₆ H ₅

100

1.6010

-

C ₁₉ H ₁₄ CLO ₄ P

g) H

C ₆ H ₅

4-FC ₆ H ₄

99.5

1.5852

-

C ₁₉ H ₁₄ FO ₄ P

h) H

C ₆ H ₅

C ₆ H ₅ CH ₂

100

1.5952

-

C ₂₀ H ₁₇ O ₄ P. The method allows one to obtain a wide range of target substances in one stage with high yields.

Description

RPCl24-ArOH

RvL-BuCl

where R, Ar and X are as defined above.

The process is carried out by boiling a mixture of equimolar amounts of organo-dichlorophosphine and the corresponding phenol in a medium of tert-butyl chloride in the presence of -. catalytic amounts of pyridine until the release of hydrogen chloride stops, after which an equimolar amount of salicylic (substituted salicylic) acid is added to the reaction mass and boiling is continued until the reaction is complete. Then, the solvent is distilled off at atmospheric and / or reduced pressure, and the target product is obtained in the residue in a practically pure way with a quantitative yield. For practical purposes, the products obtained can be used without further purification.

The resulting compounds are viscous liquids soluble in organic solvents and insoluble in water.

Example 1. Preparation of (4-mashphenoxycarbonylphenyl) phenyl 1phosphonite.

A mixture of 17.9 g (0.1 mol) of phenyldichlorophosphine, 10.8 g (0.1 mol) of 4-methylphenol and 0.079 g (1 mol) of pyridine in 50 ml of tert-butyl chloride is boiled in 2 hours before the termination of the release of hydrogen chloride. Then, 13.80 g (0.1 mol) of salicylic acid is added to the reaction mass and boiling is continued until hydrogen chloride evolution ceases (2 h). The solvent is distilled off and the residue gives 35.22 g (100%) of the desired product as a thick liquid, b.p. 217 ° C / 4 mmHg, 1.5902.

Found,%: C 68.28; H 4.59; R 9.09.

SdOnpO + RCOAf

ABOUT

Calculated,%: C 68.18; H 4.83; R 8.81.

IR spectrum (3): 2900 (CH3); 2350-2400 (RN); 1680 () j 1455-1500; 910-950 (benzene ring); 1250 (); 1120 (P-O-C arap); 750 (Р-С).

PMR spectrum (8 ppm, 1.1-1.34 d, 1H (P-H); 2.2, s, ZI (CH3C6NF); 6.8-7.9 m, 13H (C6H5, C6H4 , C6H4).

The mass spectrum of a substance is characterized by a peak of a molecular ion with M 352 intensity (I) 1% and fragment ions with m / e: 337, I 13% (M4-C1C); 264, I 14% (M + - CH C6H3); 232, I 8% (M + - CH3C6H3, P); NOC6NaC (0) OC6H4CH + t / e 228, I 15%; NOC6H4C (0) OH t / e 138, I 25%; NOC6N4CO 1 t / e 121, I 100%; OC6H4CO +, m / e 120 I 45% and C6H3ON m / e 92, I 50%.

Example 2. Preparation of 0- (2-phenoxycarbonylphenyl) phenylphosphonite.

The substance is prepared under the conditions of Example 1 from 8.95 t (0.05 mol) of phenyldichlo phosphine, 4.70 g (0.05 mol) of phenol and 6.90 g of salicylic acid. Yield 16.85 g (99.7%), bp. 215 ° C / 2 mmHg 1.6043.

Found,%: C 67.33; H 4.15; P 9.1

,

Calculated,%: C 67.46; H 4.44; R 9.17.

Example 3. Preparation of (4-chlorophenoxycarbonyl) phenyl phenylphosphonite.

Substance is prepared under the conditions of Example 1 from 8.95 g (0.05 mol) of phenyldichlorophosphine, 6.42 g (0.05 mol) of 4-chloro phenol and 6.90 g (0.05 mol) of salicylic acid. Yield 18.58 g (99.8%) p 1.6068.

Found, Z: C 61.19; H 3.70; C1 9.39; R 8.37.

With „HHC10 R.

Calculated,%: C 61.21; H 3.76; C1 9.53; R 8.32.

Example 4. Preparation of (2, 4, 4-trichlorophenoxycarbonyl) phenyl 1-phenylphosphonite.

The substance is prepared under the conditions of Example 1 from 8.95 g (0.05 mol) of phenyl dichlorophosphine, 9.87 g (0.05 mol) of 2,4,5-trichlorophenol and 6.90 g of salicylic acid. Yield 21.85 g (99%). tt 142-144 # C.

Found,%: C 51, 55; H 2.75; C1 24.03; R 7.12.

С1ГН1гС1,04Р. Calculated,%: C 5T, 64; H 2.72;

C1 24.12; R 7.02.

Example 5. Preparation of 0- (2-phenoxycarbonyl-6-methylphenyl) phenylphosphonite.

The substance is prepared under the conditions of Example 1 from 8.95 g (0.05 mol) of phenyl dichlorophosphine, 4.70 g (0.05 mol) of phenol and 7.60 g (0.05 mol) of 3-methylsalicone acid . Yield 17.60 g (100%), 1.5954.

Found,%: C 67.99; H 4.73; R 8.84.

C2pc ° 4-pCalculated,%: C 68.18; H 4.83;

R 8.81.

Example 6. Preparation of 0- (2-phenoxycarbonyl-4-chlorophenyl) phenylphosphonite.

The substance is obtained under the conditions of Example 1 from 8.95 g of phenyldichlorophosphine, 4.70 g (0.05 mol) of phenol and 8.62 g (0.05 mol) of 5-chlorosalicylic acid. Yield 18.60 g (100%), p 1.6010.

Found,%: C 61.00; H 3.73; C1 9.31; R 8.35.

C1, H14C104P;

Calculated,%: C 61.21; H 3.76; C1 9.53; R 8.32.

Example 7. Preparation of 0- (2-phenoxycarbonylphenyl) -4-fluorophenylphosphonit.

The substance is prepared under the conditions of Example 1 out of 9.85 g (0.05 mol) of 4-fluorophenyldosphorosphine, 4.70 g (0.05 mol) of phenol and 6.90 g (0.05 mol) of salicylic acid . Yield 17.7 g (99.5%), p 1.5852.

Found,%: C 63.89; H 4.12; P 8.66.

C4, H 4F041,

Calculated,%: C 64.04; H 3.93; R 8.71.

Example 8. Preparation of 0- (2-phenoxycarbonylphenyl) benzylphosphonate. The substance is obtained under the conditions of irimer 1 of 9.65 g (0.05 mol) of benzyl dichlorophosphine, 4.70 g (0.05 mol) of phenol and 6.90 g (0.05 mol) of salicylic acid. Yield 17.60 g (100%), n Ј 1.5952.

Found,%: C 68.31; H 4.79; R 8.77.

WV Calculated,%: C 68.18; H 4.83; R 8.81.

Thus, the proposed method allows, on the basis of available raw materials, to obtain a relatively large and high yield of a large assortment of previously unknown monoarylphosphonites — valuable intermediates of phosphorus – organic synthesis.

Claims (1)

Invention Formula The method of obtaining 0- (2-aryloxycarbonylphenyl) phosphonites of the general formula R 0-P ABOUT SH SOAG O 40 where R is phenyl, fluorophenyl or benzyl; Ar - unsubstituted or substituted phenyl; X is hydrogen, alkyl, halo, that is, organodichlorophosphine is reacted with an equimolar amount of the corresponding phenol in tert-butyl chloride medium in the presence of a pyridine catalyst, followed by treatment of the resulting reaction mixture with salicylic or substituted acid and the process is carried out at the boiling point of the solvent.